Metallized monoazo dyes

ABSTRACT

Metallized azo dyes of the formula ##STR1## wherein A is a sulfonyl, sulfonamido or carboxamido group, D is the residue of a phenol or naphthol, E is the residue of acetoacetanilide, a phenyl or naphthyl pyrazolone or the residue of a naphthol and M is a cation. The dyes are suitable for dyeing natural and synthetic polyamides, demonstrating good all-around fastness properties.

This application is a division of application Ser. No. 475,225, filedMay 31, 1974, now U.S. Pat. No. 4,058,515 issued Nov. 15, 1977, which isa continuation of application Ser. No. 257,645, filed May 30, 1972, nowabandoned.

BACKGROUND OF THE INVENTION

This invention relates to coppered azo dyestuffs containing a sulfonicacid group on one moiety of the molecule and a sulfonamido, sulfonyl orcarboxamido group on the other. The invention also relates to variousintermediate dyestuffs used in the preparation of these metallized dyes,to compositions, and to processes for preparing the metallizeddyestuffs. Unmetallized monoazo dyestuffs containing a sulfonic acidgroup on the coupling component and a substituted sulfonamido group onthe diazo component are known from U.S. Pat. No. 3,600,377. Althoughthese known dyestuffs have good purity and brightness of shade anddemonstrate good leveling properties, the light fastness of thesecompounds is not exceptional. Surprisingly, it has been found thatcoppering of the dyestuffs of the above-mentioned patent as well asother similar dyes produce compounds with drastically improved lightfastness and remarkable brightness of shade on polyamide fibers.

Further, coppered monoazo dyestuffs containing a sulfonic group on thecoupling component and an unsubstituted sulfonamido group on the diazocomponent are known from U.S. Pat. No. 3,511,827. These prior artdyestuffs, however, exhibit poor barre coverage as compared to themetallized dyestuffs of this invention. Furthermore, unmetallized andmetallized (chromed or coppered) monoazo dyestuffs for wool containing asulfonic group on the diazo component and an unsubstituted sulfonamidogroup on the coupling component are known from German Pat. No. 463800(Friedlander Fortschritte der Teerfarben Publikation, Vol. 16, page946). These known dyestuffs, however, have a markedly reduced affinitytoward natural and especially synthetic polyamide fibers as compared tothe dyestuffs of this invention.

It was further found that, as compared with the prior art dyestuffs asmentioned above, the metallized dyestuffs of this invention generallyhave a combination of good fastness properties, such as good lightfastness, barre coverage, leveling properties and purity and brightnessof their shades. These properties and especially good barre coverage area very important consideration in the dyeing or printing of nylon inorder to cover up irregularities. It was surprising to find that thecompounds of the instant invention, in view of the drawbacks of theprior art compounds mentioned, showed remarkable brightness of shade,good over-all fastness properties and especially excellent lightfastness and good barre coverage.

SUMMARY OF THE INVENTION

This invention, therefore, relates to metallized monoazo dyestuffscontaining a sulfonic acid group on one moiety of the molecule andsulfonamido, sulfonyl or carboxamido group on the other, tointermediates thereof, to compositions and to processes for thepreparation of said dyestuffs. These compounds are particularly suitedfor dyeing animal and artificial fibers of polyamides and polyurethanesin remarkably bright shades of red to violet and have good all-aroundfastness properties, particularly excellent light fastness and goodbarre coverage, which make them superior to similar dyes of the art.

DETAILED DESCRIPTION OF THE INVENTION

The metallized monoazo dyestuffs of this invention are those of theformula ##STR2## --SO₂ R₂ or --CONHR₃ wherein R, R₁, R₂ and R₃ are eachalkyl, hydroxyalkyl, alkoxyalkyl or hydroxyalkoxyalkyl each having up to8 carbon atoms, phenyl, phenyl-C₁₋₂ -alkylene or the latter twosubstituted on the phenyl moiety by chloro, bromo, nitro,trifluoromethyl, C₁₋₈ -alkyl or C₁₋₈ -alkoxy; R can also be hydrogen orβ-cyanoethyl; D is the residue of a phenyl or naphthol which may besubstituted by at most two chloro, bromo, C₁₋₅ -alkyl, C₁₋₅ -alkoxy,nitro or trifluoromethyl; E is the residue of an acetoacetanilide, of1-phenyl (or naphthyl)-3-methyl-5-pyrazolone or of1-phenyl-3-methyl-5-pyrazolone substituted at the phenyl moiety by 1 or2 chloro, bromo, C₁₋₅ -alkyl, C₁₋₅ -alkoxy, nitro or trifluoromethyl,whereby the --SO₃ M group is attached to the phenyl (or naphthyl) group,or the residue of a 1- or 2-naphthol; and M is hydrogen, alkali metal orammonium; and each oxygen bridge at attached in the ortho position tothe azo group. When D is the residue of a naphthol, E can also beresidue of a phenol which may be substituted by at most two chloro,bromo, C₁₋₅ -alkyl, C₁₋₅ -alkoxy, nitro or trifluoromethyl.

The more preferred metallized dyestuffs are those wherein R is hydrogen,methyl, ethyl, β-cyanoethyl or C₂₋₃ -hydroxyalkyl; R₁, R₂ and R₃ andC₁₋₈ -alkyl, phenyl or phenyl carrying up to two substituents chosenfrom C₁₋₂ -alkyl, C₁₋₂ -alkoxy and chlorine; R₂ may also be benzyl; D isthe residue of a phenol where A is attached meta or para to the oxygenbridge, the residue of a 1- or 2-naphthol where A is --SO₂ NRR₁ or --SO₂R₂ and attached in the 4- or 6-position, or the residue of a 2-naphtholwhere A is --CONHR₃ and attached in the 3-position; E is the residue of1- or 2-naphthol wherein the --SO₃ M is attached on any position otherthan 1 or 2.

In the most preferred aspect of this invention, the novel compounds maybe described by the following structural formulae ##STR3## where B isbenzyl or --NRR₁, wherein R is hydrogen, methyl, ethyl, β-cyanoethyl,β-hydroxyethyl and β- or γ-hydroxypropyl and R₁ is C₂₋₈ -alkyl, phenylor phenyl carying up to two substituents chosen from methyl, methoxy,ethoxy and chlorine; M is hydrogen, NH₄ or sodium.

The dyestuffs of the present invention may be readily prepared bytreating the corresponding unmetallized, o,o'-dihydroxy azo dyestuff orthe corresponding unmetallized o-methoxy-o'-hydroxy azo dyestuff with acopper salt in an aqueous or nonaqueous medium by known methods, such asreaction of the monoazo dyestuff with copper sulfate in the presence ofwater and sodium acetate or ammonia, or with cupric nitrate in thepresence of soda ash and an appropriate solvent such asmethylcellosolve, near the reflux temperature of the system, until thereaction is complete.

Some of the unmetallized dyestuffs used for the preparation of thecompounds of this invention are similarly novel and represent stillanother aspect of this invention. These dyestuffs may be used asintermediates as well as dyestuffs per se. As dyestuffs, they exhibitgood purity and brightness of shade, good fiber affinity and goodleveling properties. The novel unmetallized dyestuffs may be representedby the following structural formula ##STR4## wherein X and X₁ areindependently hydroxy or methoxy, ortho to the azo linkage, only one ofX and X₁ is methoxy at any one time and X₁ cannot be methoxy when E isthe residue of acetoacetanilide or of a pyrazolone; A is --SO₂ R₂ or--CONHR₃ and in any position other than ortho to X, wherein R₂, R₃, D, Eand M are as previously described and the azo linkage attaches ortho toX and X₁.

The preferred dyestuffs of the above formula correspond to the preferredmetallized dyestuffs, and one of X and X₁ is methoxy.

The metallized dyestuffs of this invention, as indicated previously, maybe prepared by diazotizing an aminobenzene compound of the formula##STR5## or a naphthylamine of the formula ##STR6## wherein X is hydroxyor methoxy ortho to the amino group, coupling the diazotized compound toa naphthol sulfonic acid or a sulfophenylmethylpyrazolone by well-knownmethods and subsequently metallizing the dyestuff.

Alternatively, the coupling can be done in reverse order by combining adiazotized orthoaminohydroxy- or orthoaminomethoxynaphthalene sulfonicacid with phenolic compounds of the formula ##STR7## or naphtholiccompounds of the formula ##STR8## wherein the hydroxy group is in 1- or2-position and A is attached in any position other than 1 or 2.

Compounds of formula (4) can also be combined with diazotizedortho-aminohydroxy- or ortho-amino-methoxybenzenesulfonic acids.

Diazo components of formula (1) and (2) above are known compounds andcan be prepared by methods well known to those skilled in the art.

For example, those compounds of formula (1) wherein X is methoxy and Ais a sulfonamido group may be prepared by treating N-acetyl-o-anisidinewith chlorosulfonic acid to obtain the corresponding sulfonyl chloridederivative. This compound is then reacted with an appropriate primary orsecondary amine and subsequently hydrolized to yield the desired aminocompound.

Those compounds of formula (1) wherein A is a sulfone and X is methoxymay be prepared by treating N-acetyl-o-anisidine with chloro-sulfonicacid to obtain the corresponding sulfonylchloride derivative, which isthen reduced to the sulfinic acid and reacted with alkylating agentslike dimethylsulfate or benzylchloride, followed by hydrolysis to yieldthe desired amino compound.

Those compounds of formula (1) wherein A is a carbamido group and X ismethoxy may for instance be prepared by combining4-methoxy-3-nitrobenzoylchloride with a primary aliphatic or aromaticamine followed by reduction of the nitro.

On the other hand, those compounds of formula (1) wherein X is hydroxyand A is a sulfonamido group can be prepared by treating, for example,ortho-nitro-chlorobenzene with chlorosulfonic acid to obtain3-nitro-4-chlorobenzenesulfonylchloride, followed by treatment with aprimary or secondary amine to yield the corresponding3-nitro-4-chlorobenzene sulfonamido derivative. This product is thentreated with caustic soda to yield the 3-nitro-4-hydroxybenzenesulfonamide and subsequently reduced to the desired3-amino-4-hydroxybenzene sulfonamide.

Furthermore, 3-nitro-4-chlorobenzenesulfonylchloride can either bereacted with benzene or properly substituted benzenes under FriedelCrafts conditions or reduced to the sulfinic acid and alkylated asmentioned above to give the corresponding arylor alkylsulfones,respectively. These are then treated with caustic soda and subsequentlyreduced to the desired 3-amino-4-hydroxybenzenesulfones.

The isomeric 4-amino-3-hydroxybenzene sulfonamides or sulfones can beprepared by treating 1,3,2-benzoxazolone with chlorosulfonic acid,converting the resulting sulfonylchloride to the desired sulfonamido orsulfone derivatives as stated above, and finally opening the oxazolonering under loss of CO₂, e.g. by a hot alkaline treatment.

Representative compounds of formula (1) that may be employed are:

N',n'-diethyl-3-amino-4-methoxybenzenesulfonamide

N'-n-butyl-3-amino-4-methoxybenzenesulfonamide

N'-(γ-methoxypropyl)-3-amino-4-methoxybenzenesulfonamide

N'-methyl-3-amino-4-methoxybenzenesulfonamide

3-amino-4-methoxyphenylbenzylsulfone

3-amino-4-methoxybenzanilide

2-amino-4-(methylsulfonyl)phenol

4-amino-3-hydroxy-4'-chlorobenzenesulfonanilide and

4-amino-2,5-dimethoxy-3'-trifluoromethylbenzenesulfonanilide.

Compounds of formula (2) may be suitably prepared, for example, asfollows:

When X is methoxy, by treating the proper nitro-methoxy- oracylamino-methoxy-naphthalenesulfonyl chlorides as described above forbenzenesulfonyl chloride derivatives, followed by reduction orhydrolysis, respectively.

When X is hydroxy, by reacting a coupler of formula (4) with a diazoniumcompound and reducing the resulting azo compound.

The couplers of formula (3) and (4) can be obtained from thecorresponding hydroxybenzene- or hydroxynaphthalenesulfonic acids,(after protection of the hydroxy group, e.g. by acylation with aceticanhydride etc.) by conversion to the sulfonyl chlorides and furtherreaction to the sulfonamides or sulfones as mentioned before followed bydeacylation. Proper carbonamides are formed from correspondinghydroxybenzene- or hydroxynaphthalene carboxylic acids via theircarbonylchlorides by a similar route.

Another general method of preparation for the couplers of formula (3)and (4) is the diazotization of the proper aminobenzene- oramino-naphthalenesulfonamides, -sulfones and -carbonamides andsubsequent treatment of the resulting diazonium compounds at elevatedtemperatures.

Representative compounds of formula (2) that may be employed are:

1-amino-2-methoxynaphthalene-o-sulfon-o-anisidide

1-amino-2-hydroxynaphthalene-6-N'-methyl-N'-(β-hydroxyethyl) sulfonamide

1-amino-2-hydroxynaphthalene-7-N-piperidylsulfonamide

1-amino-2-hydroxy-4-(methylsulfonyl)naphthalene

2-amino-1-hydroxynaphthalene-3-sulfonamide

2-amino-1-hydroxynaphthalene-4-N'-isopropylsulfonamide

2-amino-1-hydroxy-5-(benzylsulfonyl)naphthalene and2-amino-1-hydroxynaphthalene-6-N',N'-di-(β-hydroxyethyl)sulfonamide.

Representative naphthol and pyrazolone couplers are:

2',3', or 4'-sulfo-1-phenyl-3-methyl-5-pyrazolone

2'-chloro-5'-sulfo-1-phenyl-3-methyl-5-pyrazolone

2'-5'-dichloro-4'-sulfo-1-phenyl-3-methyl-5-pyrazolone

6'-chloro-2'-methyl-4'-sulfo-1-phenyl-3-methyl-5-pyrazolone

2'-methyl-4'-sulfo-1-phenyl-3-methyl-5-pyrazolone

1-(6'-sulfonaphthyl-2-)-3-methyl-5-pyrazolone

1-hydroxynaphthalene-3,4,5,6 or 7-sulfonic acid and

2-hydroxynaphthalene-5,6,7 and 8-sulfonic acid.

Representative compounds of formulae (3) and (4) are:

1-hydroxybenzene-4-sulfon-o-toluidide

N'-(β-cyanoethyl)-4-hydroxybenzenesulfonanilide

1-hydroxy-4-(benzylsulfonyl)benzene

4-hydroxy-3'-nitrobenzanilide

1-hydroxynaphthalene-3-N'-ethylsulfonamide

1-hydroxynaphthalene-4-N'-isopropylsulfonamide

1-hydroxy-5-(benzylsulfonyl)naphthalene

1-hydroxynaphthalene-6-N'-(β-hydroxylethyl)sulfonamide

2-hydroxynaphthalene-5-N'-(β-ethylhexyl)sulfonamide2-hydroxynaphthalene-6-N'-(cyclohexyl)sulfonamide

2-hydroxynaphthalene-6-N'-methyl-N'-(β-hydroxyethyl)sulfonamide

2-hydroxy-6-(methylsulfonyl)naphthalene

2-hydroxynaphthalene-7-N'-(γ-methoxypropyl)sulfonamide

3-hydroxy-2-naphthanilide and

3-hydroxy-2-naphth-o-anisidide.

Representative diazotisable amines for the reverse order coupling are:

1-amino-2-hydroxynaphthalene-4,5,6,7 or 8-sulfonic acid

1-amino-2-methoxynaphthalene-6-sulfonic acid

2-amino-1-hydroxynaphthalene-3,4,5,6 or 7-sulfonic acid

2-amino-4-methoxybenzenesulfonic acid

3-amino-4-hydroxybenzenesulfonic acid

3-amino-4-hydroxy-6-methylbenzenesulfonic acid

3-amino-4-hydroxy-6-chlorobenzenesulfonic acid

4-amino-3-hydroxybenzenesulfonic acid and

4-amino-2,5-dimethoxybenzenesulfonic acid.

The metallized monoazo dyestuffs are particularly suitable for thedyeing of nylon material in aqueous dyebaths at pH values of 4 to 8,preferably 5 to 7, and at liquor ratios of 20:1 to 50:1. The initial pHis adjusted to the desired value by the addition of a suitable acid,such as acetic acid or alkali, such as sodium carbonate. Preferably thedyebath is buffered during the dyeing cycle with a suitable bufferingagent such as a mixture of monosodium phosphate and disodium phosphate.The amount of dyestuff used will depend on the depth of shade requiredand will range from 0.05% for light shades to 2.0% for heavy shadescalculated on the weight of fiber taken. The temperature during thedyeing cycle may range from 80° to 100° C., preferably 95°-100° C. andthe duration of the cycle from 15 minutes to 2 hours, preferably 45minutes to 75 minutes.

The following examples are given by way of illustration.

EXAMPLE 1

27.8 parts 3-amino-4-methoxy-benzenesulfonanilide are dissolved in 500parts water at 70° C. containing 49 parts of 10 N hydrochloric acid. Thesolution obtained is cooled to 0° C. to 5° C. and diazotized by theaddition of an aqueous solution containing 7 parts sodium nitrite. Theresulting diazo solution is gradually added to a stirred and icedsolution of 22.4 parts 2-naphthol-6-sulfonic acid in 800 parts watercontaining 40 parts soda ash. The coupling mass is stirred for 1 hour at5°-10° C. and the dyestuff isolated by the addition of 5% salt (byvolume). The dyestuff is filtered off and dried.

5.35 parts of the monoazo dyestuff, 2.7 parts cupric nitrate, 0.56 partssoda ash and 40 mls. methyl cellolsolve are brought to gentle reflux andheld at refluxing temperature for 10 hours. The reaction mixture is thencooled and filtered. The filter cake is washed with 5 mils. methylcellosolve. The filter cake is then reslurried in 85 parts of 3% brineat room temperature for 1 hour and filtered, washed with 10 parts of a5% brine solution and dried at 65°-70° C. The dyestuff thus produced hasthe formula ##STR9## and dyes nylon from neutral or weakly acid dyebathsin bluish red shades with excellent light fastness and good washfastness and barre coverage.

EXAMPLE 2

26.4 parts of 2-aminophenol-4-sulfonanilide are dissolved in 155 partswater at 35° C. containing about 9 parts of caustic soda to pH˜12.0 andthe resulting solution clarified. The residue is washed with about 65parts water and the clarified liquor and washings combined to give atotal volume of about 250 mls. A solution of 7 parts sodium nitrite in20 parts water are added. The clarified liquor containing sodium nitriteis then added gradually during 1 hour into a mixture of 46.5 parts 10 Nhydrochloric acid, 250 parts cold water and 350 parts of ice. Themixture is stirred for 30 minutes at -2° C. to 0° C. The excess nitriteis removed by the addition of a small quantity of sulfamic acid and thepH of the yellow precipitated diazo product is raised to about 3 byaddition of about 5.5 parts soda ash.

The resulting diazo mixture is gradually added, with stirring, at 0° C.to 2° C. to an iced solution of 22.4 parts 2-naphthol-6-sulfonic acid in800 parts water containing 40 parts soda ash. The coupling mass is thenstirred overnight to room temperature (pH 9.5) and the dyestuff isisolated by the addition of salt (5% by volume). The dyestuff isfiltered and washed with 500 parts of a 10% brine solution and thendried.

10.4 parts of the dried monoazo dyestuff are slurried in 100 parts waterat 75° C. The pH is reduced to about 4.9 by addition of 1.5 partsglacial acetic acid.

5 parts of copper sulfate dissolved in 20 parts water are added and thepH readjusted to 4.0-4.5 by addition of about 4 parts sodium acetate.The mixture is heated to 90°-95° C. in 30 minutes and held at 90°-95° C.for 2 hours. The resulting product is filtered hot and the filter cakewashed with 25 parts of 2% brine solution and then dried. The dyestuffthus produced is the same as that from Example 1.

EXAMPLE 3

When the reaction is Example 1 is carried out using an equivalent amountof N'-n-butyl-3-amino-4-methoxy-benzenesulfonamide in place of3-amino-4-methoxybenzenesulfonanilide a similar dyestuff is obtainedwith the formula ##STR10## which dyes nylon in bright bluish red shadesfrom weakly acid dyebaths with excellent light fastness and good barrecoverage.

EXAMPLE 4

A similar dyestuff is obtained if an equivalent quantity of3-amino-4-methoxy-N'-2-ethylhexylbenzenesulfonamide is used in place of3-amino-4-methoxybenzenesulfonanilide in Example 1. The dyestuff has theformula ##STR11## and dyes nylon from neutral or weakly acid dyebaths inbluish red shades with good fastness properties.

Similarly when N',N'-dibutyl-3-amino-4-methoxybenzenesulfonamide,N'-(β-hydroxyethyl)-3-amino-4-methoxybenzenesulfonanilide,N'-(γ-methoxypropyl)-3-amino-4-methoxybenzenesulfonamide,N'-(β-cyanoethyl)-3-amino-4-methoxy-4'-chlorobenzenesulfonanilide,3-amino-4-methoxy-3'-nitrobenzenesulfonanilide,3-amino-4-methoxy-4'-trifluoromethylbenzenesulfonanilide,3-amino-4-methoxy-2'-ethylbenzenesulfonanilide, orN'-ethyl-3-amino-4-methoxy-4'-methoxybenzenesulfonanilide is used inplace of 3-amino-4-methoxybenzenesulfonanilide in the above example, theappropriately substituted dyestuff is obtained.

EXAMPLE 5

25.8 parts of ground N'-n-butyl-3-amino-4-methoxybenzenesulfonamide aredissolved in a mixture of 75 parts water and 29 parts 10 N hydrochloricacid. The solution is brought to 0° C. with 75 parts of ice anddiazotized by the rapid addition of a solution of 7 parts sodium nitritein 20 parts water. The diazo is stirred for 11/2 hours at 2° C. to 5° C.and then clarified. The clarified diazo is then added gradually to astirred and iced solution of 22.4 parts 1-naphthol-4-sulfonic acid in600 parts water containing 40 parts of soda ash. The reaction mixture isstirred for 1 hour at 2°-5° C. and the dyestuff is then salted out byaddition of 3% salt (based on volume) and filtered. The filter cake isthen washed with 100 parts of 3% brine solution and dried.

5.15 parts of the dried monoazo dyestuff are stirred into a mixture of 5parts cupric nitrate, 3.06 parts soda ash and 50 mls. methyl cellosolve.The reaction mixture is heated to reflux and held at reflux for 18hours. The reaction mixture is then cooled to room temperature andfiltered. The filter cake is reslurried in 75 parts water and completelyprecipitated from the liquor by addition of 16.5 parts common salt. Theresulting precipitate is filtered and dried at 65°-70° C. The dyestuffthus produced has the formula ##STR12## and dyes nylon from a neutral orweakly acid dyebath in bright reddish-violet shades with good lightfastness and good barre coverage.

EXAMPLE 6

5.4 parts of the monoazo dyestuff, obtained by couplingN'-n-hexyl-3-amino-4-methoxybenzenesulfonamide with1-naphthol-4-sulfonic acid, is refluxed for 15.5 hours in 40 mls. methylcellosolve containing 3.2 parts cupric nitrate and 1.06 parts soda ash.The reaction product is filtered off after cooling to room temperatureand the resulting filter cake reslurried in 90 parts water containing3.7 parts common salt for 30 minutes. The filter cake isolated byfiltration is washed with 20 parts of a 5% sodium chloride solution anddried. The dyestuff obtained has the following formula ##STR13## anddyes nylon in bright reddish-violet shades with excellent lightfastness, good leveling properties and fair barre coverage.

Similarly, when the 3-amino-4-methoxybenzenesulfonamides mentioned atthe end of Example 4 are used in place ofN'-n-hexyl-3-amino-4-methoxybenzenesulfonamide, the appropriatelysubstituted dyestuffs are obtained.

EXAMPLE 7

When N'-n-butyl-3-amino-4-methoxybenzenesulfonamide is replaced by anequivalent amount of 3-amino-4-methoxyphenylbenzylsulfone in Example 5,a similar dyestuff is obtained having the formula ##STR14## which dyesnylon from neutral to weakly acid dyebaths in bright bluish red shadeswith excellent light fastness and barre coverage, and good levelingproperties.

Similarly, when 3-amino-4-methoxyphenyl-phenethylsulfone,3-amino-4-methoxyphenyl-n-butylsulfone,3-amino-4-methoxyphenyl-3'-methoxypropylsulfone or3-amino-4-methoxyphenyl-p'-tolylsulfone is used in place of3-amino-4-methoxyphenyl-benzylsulfone, the appropriately substituteddyestuff is obtained.

Similarly, when the above-mentioned 3-amino-4-methoxyphenylsulfones arecombined with 2-naphthol-6-sulfonic acid and coppered, thecorrespondingly substituted dyestuffs are obtained.

EXAMPLE 8

15.18 parts of dry monoazo dyestuff, obtained by couplingN',N'-diethyl-3-amino-4-methoxybenzenesulfonamide with1-naphthol-4-sulfonic acid according to Example 5, is stirred into 6.8parts cupric nitrate, 2.6 parts soda ash in 100 mls. methyl cellosolve.The reaction mixture is heated to reflux and held at reflux for 16 hoursand then allowed to cool to room temperature. The product is filteredand washed with 40 mls. methyl cellosolve. The filter cake is rechargedinto 140 parts water containing 10 parts of common salt, stirred for 30minutes at room temperature, refiltered and dried. The dyestuff has theformula ##STR15## and dyes nylon in bright reddish violet shades withexcellent light fastness and good barre coverage.

EXAMPLE 9

26.4 parts 2-aminophenol-4-sulfonanilide are coupled to 22.4 parts of1-naphthol-4-sulfonic acid according to the procedure described inExample 2. 10.4 parts of the dried monoazo dyestuff thus obtained aretreated with 5 parts copper sulfate in 20 parts water at 90°-95° C.according to the procedure of Example 2. The dyestuff has the formula##STR16## which dyes nylon in bright bluish red shades with good lightfastness and barre coverage.

Similarly, when N'-isopropyl-2-aminophenol-4-sulfonamide,N',N'-methylbutyl-2-aminophenol-4-sulfonamide,N'-(β-hydroxypropyl)-2-aminophenol-4-sulfonamide,N'-(β-hydroxyethyl)-2-aminophenol-4-sulfonanilide,2-aminophenol-4-sulfon-o-chloro-o'-toluidide or2-aminophenol-4-sulfon-2',5'-dimethoxyanilide is used in place of2-aminophenol-4-sulfonanilide, the appropriately substituted dyestuff isobtained.

Similarly, when the above-mentioned 2-aminophenol-4-sulfonamides arecombined with 2-naphthol-6-sulfonic acid and coppered, thecorrespondingly substituted dyestuffs are obtained.

EXAMPLE 10

18.7 parts 2-aminophenol-4-methylsulfone are dissolved in 230 partswater at 65° C. containing 18.5 parts 10 N hydrochloric acid solution.The solution is iced to 0° C. by the addition of about 250 parts ice andthen diazotized by the addition of 7 parts sodium nitrite dissolved in20 parts water. The diazo is stirred at 5°-8° C. for 30 minutes and thevolume adjusted to 700 mls. with ice and water. The diazo solution isthen added gradually during 30 minutes to a stirred and iced solution of22.4 parts 1-naphthol-4-sulfonic acid in 200 parts water containing 40parts soda ash and 10 parts 1-naphthalenesulfonic acid, sodium salt. Thecoupling mass is then stirred overnight to room temperature andfiltered. The filter cake is washed with 200 parts of 7.5% brinesolution and dried.

8.9 parts of the dried monoazo dyestuff are treated with an aqueoussolution containing 5 parts copper sulfate at pH 4.6 as described inExample 2 to yield a dyestuff with the following formula ##STR17## whichdyes nylon in reddish violet shades with excellent light fastness andgood barre coverage and leveling properties.

Similarly, when 2-aminophenol-4-ethylsulfone,2-aminophenol-4-(3'-methoxypropyl)sulfone,2-aminophenol-4-phenylsulfone, 2-aminophenol-4-p'-chlorophenylsulfone,2-aminophenol-4-m-CF₃ -phenylsulfone,2-aminophenol-4-(o-nitrophenyl)sulfone or2-aminophenol-4-2',4'-xylyl-sulfone is used in place of2-aminophenol-4-methylsulfone, the appropriately substituted dyestuff isobtained.

EXAMPLE 11

A similar dyestuff is obtained when 1-naphthol-4-sulfonic acid isreplaced by 2-naphthol-6-sulfonic acid in Example 10. The dyestuff hasthe formula ##STR18## which dyes nylon in bluish red shades with goodlight fastness and leveling properties and good barre coverage.

Similarly, when the 2-aminophenol-4-sulfones mentioned at the end ofExample 9 are combined with 2-naphthol-6-sulfonic acid and coppered, thecorrespondingly substituted dyestuffs are obtained.

EXAMPLE 12

4.99 parts of the monoazo dyestuff, obtained by coupling3-amino-4-methoxybenzanilide with 1-naphthol-4-sulfonic acid, isrefluxed for 24 hours in 40 mls. methyl cellosolve containing 5.7 partscupric nitrate and 1.26 parts soda ash. The reaction product is filteredafter cooling to room temperature and the filter cake is reslurried in150 parts water. The slurry is filtered and the filter cake washed with25 parts water and dried. The dyestuff obtained has the formula##STR19## and dyes nylon from neutral dyebaths in bright reddish violetshades with excellent light fastness, good leveling properties and fairbarre coverage.

Similarly, when N'-n-butyl-3-amino-4-methoxybenzamide,N'-(β-hydroxyethyl)-3-amino-4-methoxybenzamide,N'-(γ-methoxypropyl)-3-amino-4-methoxybenzamide,3-amino-4-methoxy-4'-chlorobenzanilide,3-amino-4-methoxy-2'-nitrobenzanilide,3-amino-4-methoxy-4'-trifluoromethylbenzanilide or3-amino-4-methoxy-4'-ethoxybenzanilide is used in place of3-amino-4-methoxybenzanilide in the above example, the appropriatelysubstituted dyestuff is obtained.

EXAMPLE 13

25.8 parts of N',N'-diethyl-3-amino-4-methoxybenzenesulfonamide arediazotized as described for the amine in Example 5 and the resultingdiazo solution is combined with a chilled mixture of 25.4 parts ofm-sulfophenylmethylpyrazolone in 200 parts of water, 8 parts of causticsoda, 20 parts of soda ash and ice. 5 parts of salt per 100 parts ofvolume are added one hour later and the monoazo dyestuff is filtered offin a good form after heating to 85° C.

This monoazo dyestuff is stirred into a mixture of 400 parts of methylcellosolve, 25 parts of cupric nitrate trihydrate and 5.2 parts of sodaash, heated and held at 116°-118° C. for four hours. The reaction massis cooled and diluted with an equal volume of water. The metallizeddyestuff is precipitated with 50 parts of salt, filtered and dried. Ithas the formula ##STR20## and dyes nylon in very light fast shades oforange.

Similarly, when using 4'-sulfophenyl-, 2'-chloro-5'-sulfo-phenyl-,2'-methyl-4'-sulfo-phenyl-, or 6'-sulfo-2'-naphthylmethyl-pyrazolone inplace of m-sulfophenylmethylpyrazolone, the appropriately substituteddyestuff is obtained.

Similarly, when replacingN',N'-diethyl-3-amino-4-methoxybenzene-sulfonamide with N'-n-pentyl-,N'-m-nitrophenyl-, orN'-p-ethoxyphenyl-3-amino-4-methoxybenzenesulfonamide, with3-amino-4-methoxybenzene-benzylsulfone, or with3-amino-4-methoxybenzanilide, the appropriately substituted dyestuff isobtained.

EXAMPLE 14

26.4 parts of 2-aminophenol-4-sulfonanilide are diazotized as describedin Example 2 and gradually added to a chilled solution of 26 parts ofacetoacetanilide-p-sulfonic acid and 30 parts of soda ash in 200 partsof water. Stirring is continued overnight while the temperature rises to18° C.

The product is precipitated with hydrochloric acid at pH 7.4, decanted,purified from 40% aqueous methanol containing 6% salt and dried. 11parts of product thus obtained are coppered as described in Example 2.The resulting dyestuff has the formula ##STR21## and dyes nylon in fastyellow shades.

Similarly, when acetoacetanilide-m-sulfonic acid,acetoacetanilide-4'-methoxy-3'-sulfonic acid,acetoacetanilide-2'-chloro-4'-sulfonic acid oracetoacet-2'-naphthylamide-6'-sulfonic acid is used in place ofacetoacetanilide-p-sulfonic acid, the appropriately substituted dyestuffis obtained.

Similarly, when 2-aminophenol-4-sulfonanilide is replaced by2-aminophenol-4-sulfopiperidide, 2-aminophenol-4-benzylsulfone or2-aminophenol-4-(n-octylcarbamide), the appropriately substituteddyestuff is obtained.

EXAMPLE 15

A mixture of 29.3 parts of 3-hydroxy-2-naphth-o-anisidide and 100 partsof hot water is made alkaline with 6 parts of caustic soda and cooled to30° C. 25 parts of "diazo acid"[naphth(1,2-d)(1,2,3)oxadiazole-5-sulfonic acid] is added in portions,the pH is adjusted to 11 with acetic acid and stirring is continued for20 hours. The product is filtered off at 46° C. and washed with 3% saltsolution.

5.65 parts of dried monoazo dyestuff thus obtained, 2.5 parts of coppersulfate pentahydrate and 1.75 parts of sodium acetate are stirred in 90parts of water at 70°-90° C. for 2 hours. 30 parts of 25% salt solutionare added. The precipitate is filtered at 71° C., washed with 5% and 3%salt solution, and dried. Some impurity is removed with hot chloroform.A metallized dyestuff is obtained which has the formula ##STR22## anddyes nylon from neutral or weakly acid dyebaths in level and brightbluish violet shades of excellent light fastness.

EXAMPLE 16

When 3-hydroxy-2-naphth-o-anisidide and diazo acid in the precedingexample are replaced by 27.7 parts of 3-hydroxy-2-naphtho-o-toluidideand 29.5 parts of "nitrodiazo acid"[7-nitronaphth(1,2-d)(1,2,3)oxadiazole-5-sulfonic acid], respectively,and 6 parts of the dried coupling product are coppered, a dyestuff ofthe formula ##STR23## is obtained which dyes nylon in redder violetshades.

EXAMPLE 17

25.3 parts of 1-amino-2-methoxynaphthalene-6-sulfonic acid is dissolvedin 200 parts of water at 42° C. and caustic alkali to attain pH 7.6. Iceis added to cool to 2° C., followed by 20 parts of concentratedhydrochloric acid and sufficient alkali nitrate, as concentrated aqueoussolution, to achieve complete diazotization.

This diazo preparation is stirred during one-half hour into a chilledmixture of 26.3 parts of 3-hydroxy-2-naphthanilide, 100 parts of waterand excess caustic alkali. The temperature is permitted to rise andstirring is continued overnight at room temperature. 150 parts of 25%salt solution is added after heating to 70° C. and the monoazo dyestuffis isolated by filtration, washed with 300 parts of 3% salt solution anddried.

5.6 parts of this monoazo dyestuff is heated in 80 parts ofmethylcellosolve together with 0.65 parts of soda ash and 2.9 parts ofcupric nitrate trihydrate. A temperature of 112° to 118° C. ismaintained for 20 hours while successive additions of 1.5 parts ofcupric nitrate, 0.1 part of soda ash and 4 parts of pyridine are made.The metallized product is filtered after cooling to room temperature,washed with 5 parts of methyl cellosolve, reslurried in 100 parts ofwater at 50° C., refiltered and dried. It has the formula ##STR24## anddyes nylon from neutral or weakly acid dyebaths in bright violet shades.

EXAMPLE 18

When 29.3 parts of 3-hydroxy-2-naphth-o-anisidide is used in place ofthe anilide of the preceding example, and 5.8 parts of the driedcoupling product are coppered, a similar dyestuff obtains with theformula ##STR25##

EXAMPLE 19

20.3 parts of 3-amino-4-methoxybenzenesulfonic acid are dissolved weaklyalkaline in 80 parts of water and diazotized under 10° C. by thesuccessive addition of 30 parts of concentrated hydrochloric acid and 7parts of sodium nitrite, as concentrated aqueous solution. This diazopreparation is stirred during 2 hours into a mixture of 30 parts of2-hydroxynaphthalene-6-sulfonanilide, 100 parts of water and 5.3 partsof caustic soda at 5° C. When the coupling is finished, the suspensionis diluted to 600 parts volume with water, the pH is reduced to 9.5,some salt is added, and the product is filtered. The filter cake isreslurried in 600 parts of water at 70° C., filtered off again, washedwith 300 parts of 2% salt solution at 60° C., and dried.

5.5 parts of this monoazo dyestuff is stirred in 80 parts ofmethylcellosolve together with 3.4 parts of cupric nitrate trihydrateand 0.75 parts of soda ash at 116° to 120° C. for 5 hours. Aftercooling, 90 parts of 15% salt solution are added and the metallizedproduct is filtered at 37° C., washed with 75 parts of 3% salt solutionand dried. It has the formula ##STR26## and dyes nylon from neutral orweakly acid dyebaths in bright bluish red shades.

EXAMPLE 20

When 1-hydroxynaphthalene-4-sulfonanilide is used in the precedingexample in place of 2-hydroxynaphthalene-6-sulfonanilide, a similardyestuff is obtained with the formula ##STR27##

Similarly, when the sulfonanilides of Examples 19 and 20 are replaced bythe corresponding hydroxynaphthalene-N',N'-dimethylsulfonanilides;-N'-n-hexylsulfonanilides; -N'-methyl-N'-(β-hydroxyethyl)sulfonanilides;-N'-(β-hydroxyethyl)sulfonanilides; -sulfon-chloroanilides;-sulfontoluidides; -N'-ethylsulfonanisidides, or thehydroxynaphthalene-methyl, ethyl, or benzyl-sulfones, dyestuffs of thecorresponding structures are obtained.

EXAMPLE 21

When the 3-amino-4-methoxybenzenesulfonic acid diazo preparation inExample 19 is replaced by the 1-amino-2-methoxynaphthalene-6-sulfonicacid diazo preparation of Example 17, a dyestuff obtains with theformula ##STR28##

Similarly, when 2-hydroxynaphthalene-6-sulfonanilide is replaced by thecouplers listed under Example 20, dyestuffs of the correspondingstructures are obtained.

EXAMPLE 22

The diazo preparation of Example 19 is added to a chilled mixture of26.3 parts of 3-hydroxy-2-naphthanilide, 160 parts of water and excesscaustic soda during one and a half hours. Stirring is continued forseveral hours while the temperature is allowed to rise. The pH iseventually reduced to 10 with bicarbonate and the monoazo dyestuff isfiltered, washed with 3% salt solution and dried. 5.6 parts of thismonoazo dyestuff and 3.2 parts of cupric acetate monohydrate are stirredin 60 parts of water at 90°-95° C. for 12 hours. The metallized productis filtered at 90° C., washed with 25 parts of 5% aqueous salt solutionand dried. It has the formula ##STR29## and dyes nylon from neutral orweakly acid dyebaths in bluish red shades.

The following dyestuffs may be similarly prepared from one or more ofExamples 1-22.

EXAMPLE 23 ##STR30## EXAMPLE 24 ##STR31## EXAMPLE 25 ##STR32## EXAMPLE26 ##STR33## EXAMPLE 27 ##STR34## EXAMPLE 28 ##STR35## EXAMPLE 29##STR36## EXAMPLE 30 ##STR37## EXAMPLE 31 ##STR38## EXAMPLE 32 ##STR39##EXAMPLE 33 ##STR40## EXAMPLE 34 ##STR41## EXAMPLE 35 ##STR42## EXAMPLE36 ##STR43## EXAMPLE 37 ##STR44## EXAMPLE 38 ##STR45## EXAMPLE 39##STR46## EXAMPLE 40 ##STR47## EXAMPLE 41 ##STR48## EXAMPLE 42 ##STR49##EXAMPLE 43 ##STR50## EXAMPLE 44 ##STR51## EXAMPLE 45 ##STR52## EXAMPLE46 ##STR53## EXAMPLE 47 ##STR54## EXAMPLE 48 ##STR55## EXAMPLE 49##STR56## EXAMPLE 50 ##STR57## EXAMPLE 51 ##STR58## EXAMPLE 52 ##STR59##EXAMPLE 53 ##STR60## EXAMPLE 54 ##STR61## EXAMPLE 55 ##STR62##

When the above-described preparations are carried out with potassiumsalts and caustic potash in place of sodium salts and caustic soda, thepotassium salts of the corresponding dyestuffs are obtained.

EXAMPLE 56

To obtain the dyes in the form of their free acids, an aqueoussuspension of an instant dye is rendered strongly acid with a mineralacid, e.g. concentrated hydrochloric acid, or sulfuric acid and theinsoluble acid form of the dye is separated by filtration.

The free acid form of the dye can be neutralized with other bases, asfor example lithium hydroxide, lithium carbonate or ammonia, to form dyesalts containing the corresponding cations, as desired.

EXAMPLE 57

Into an aqueous dyebath containing 4000 parts by weight of water, 0.25parts of the dyestuff described in Example 1, 1 part of nonionic wettingagent, nonylphenyl-polyethyleneglycol ether [ethyleneoxide condensationproduct of nonylphenol (TERGITOL-NPX Union Carbide)], 6 parts ofmonosodium phosphate and 0.75 parts of disodium phosphate, to maintain apH of 6.0, 100 parts of nylon fabric are entered at 60° C. Thetemperature is raised to 100° C. and held at 100° C. for 1 hour whilethe fabric is mildly agitated to assure uniform dyeing. The fabric isthen removed from the bath, rinsed with cold water, and dried. It isdyed a very even and fast shade of bluish red.

EXAMPLE 58

The procedure of Example 57 is repeated with 0.5 parts of the dyestuffsdescribed in Examples 4, 5, 6, 8, 11, 12, and 21, respectively. Oneobtains even and fast shades of bluish red.

EXAMPLE 59

The procedure of Example 57 is repeated with 1.0 part of the dyestuffsdescribed in Examples 15, 16, 17 and 18, respectively. One obtains fastand even shades of violet.

EXAMPLE 60

Into an aqueous dyebath containing 4000 parts of water, 0.1 to 1.0 partsof the dyestuffs described in Examples 3, 7 and 9, respectively, or amixture of them totaling 0.1 to 1.0 parts, one part of nonionic wettingagent, 10 parts of anhydrous sodium sulfate, and 10 parts of aceticacid, 100 parts of nylon fabric are entered at 60° C. The temperature israised to 96° C. in 45 minutes and held at 96° C. for 1 hour while thefabric is mildly agitated. The fabric is then removed from the bath,rinsed with cold water and dried. It is dyed very even and fast shadesof bluish red.

EXAMPLE 61

This example and Example 62 illustrate the use of the dyestuffsdescribed in this application in differential dyeing nylon anddemonstrate their utility in the differential dyeing of nylon carpeting.Into an aqueous dyebath containing 200 parts water at 40° C., 0.006parts of the dyestuff described in Example 9, 2 parts of a nonionicwetting agent (Tergitol NPX, Union Carbide, a nonylphenyl polyethyleneglycol ether), buffered at pH 6 with 0.4 parts sodium dihydrogenphosphate and 0.075 parts disodium hydrogen phosphate is entered 5 partsof Multi-Fabric Test Fabric Style 11 (Test Fabric, Inc.), constructed ofstripes of cationic-dyeable nylon (Nylon 844, E. I. du Pont de Nemours,Inc.), light acid-dyeable nylon (Nylon 845, du Pont), normalacid-dyeable nylon (Nylon 846, du Pont) and deep acid-dyeable nylon(Nylon 847, du Pont). The temperature is raised to 96° C. in 20 minutesand held at 96° C. for 1 hour while the fabric is mildly agitated. Thefabric is removed from the bath, rinsed with cold water and dried. Thecationic-dyeable Nylon 844 is reserved white while the acid-dyeableNylons 845, 846 and 847 showed excellent contrast, the depth of shadebeing approximately in the ratio of 0.05:0.2:1.1 for Nylons 845, 846 and847, respectively. This example illustrates the use of the dyestuff inExample 9 for the dyeing of differential dyeing nylon carpeting.

EXAMPLE 62

The procedure of Example 61 is repeated using 0.00825 parts of thedyestuff of Example 4 in place of 0.006 parts of the dyestuff of Example9. A similar result is obtained.

We claim:
 1. Polyamide fibers dyed with a compound of the formula##STR63## wherein B is benzyl or --NRR₁, wherein R is selected from thegroup consisting of hydrogen, methyl, ethyl, β-cyanoethyl,β-hydroxyethyl, β-hydroxypropyl and γ-hydroxypropyl; and R₁ is C₂₋₈-alkyl, phenyl or phenyl carrying up to two substituents selected fromthe group conssisting of methyl, methoxy, ethoxy and chlorine; M ishydrogen, NH₄ or sodium; and the positions of the oxygen bridge, the azolinkage and the sulfonic acid group on the naphthol residue is either1-2-4 or 2-1-6, respectively.
 2. The polyamide fibers of claim 1,wherein the compound is of the formula ##STR64##
 3. The polyamide fibersof claim 1, wherein the compound is of the formula ##STR65##
 4. Thepolyamide fibers of claim 1, wherein the compound is of the formula##STR66##
 5. The polyamide fibers of claim 1, wherein the compound is ofthe formula ##STR67##